US20110005428A1 - Silver organo-sol ink for forming electronically conductive patterns - Google Patents

Abstract

The present invention relates to solution type silver organo-sol ink for forming electrically conductive patterns. The present invention provides silver organo-sol ink of solution type for forming electrically conductive pattern comprising effective amount of silver aromatic carboxylate and a reactive organic solvents, which can form chelate or complex with silver, are, for example, organic solvents having keton, mercapto, carboxyl, aniline or sulfurous functional group, substituted or unsubstituted. By the present invention, silver organo-sol ink of solution type basically having higher content of silver is obtained. The solution type ink of the present invention can be used for forming conductive patterns in flat panel display such as plasma display panel(PDP) to reduce the numbers of steps for pattern forming drastically.

Description

TECHNICAL FIELD
• The present invention relates to silver organo-sol ink, more specifically solution type silver organo-sol ink for forming electrically conductive patterns.
BACKGROUND ART
• Pattern forming technologies used in semiconductor and display industries are classified into 3 categories. One is a subtractive method mainly applied to thin film technologies such as CVD, PVD and sputtering wherein a metal layer is deposited on a substrate, a photo-resist layer is patterned by lithography on the metal layer, and then the metal layer is etched as a pattern. Another is an additive method used in thick film technologies such as screen-printing. The other is a subtractive-additive method adopting both of a subtractive method and an additive method. Pattern forming by an additive method is an economic process, which spares material and decreases number of steps, but additive methods of thick film technologies such as screen-printing are not so fine as thin film technologies, and thus are applied to different processes.
• If an additive method accomplishes finer patterns, it is more favorable in aspects of environment and cost reduction. For example, attempts to apply an additive method to pattern forming for color filters originally formed by thin film technologies have been made. In this context, pattern forming by inkjet printing has been recently noted.
• MOD material has been researched since Vest, R.W. tested inks made of MOD material (IEEE Transactions on Components, Hybrids and Manufacturing Technology, 12(4), 545-549, 1987). Kydd, et al in WO98-37133 disclosed inkjet-printing ink consisting of MOD material and particulate metal. U.S. Pat. No. 6,878,184 owned by Kovio Inc. disclosed metal ink of nano-size particle prepared from MOD and a reductant (for example, aldehydes). Many attempts have been made to use ink containing dispersed fine metal particles, especially silver particles for forming electrically conductive pattern. A new inkjet-printing system including nozzles should be devised with inks dispersed with fine metal particles, i.e., fine silver particles because those behave differently from ordinary inks. In addition, additives added to sustain suspension would do harm to the physical properties of patterns formed.
• In the above-mentioned respect, inks containing MOD (metallo-organic de-composition material)can be applied to traditional inkjet printing devices without severe modification of the system if those are thoroughly solution. Solution inks containing MOD, in addition, can lower the temperature of metalization, and thus can be applied on flexible substrates such as plastic.
• Korean Patent Publication No. 2004-85470 applied by Haeuncomtec disclosed a metal ink for inkjet-printing consisting of 5˜40t % of silver oxide, 10-20 wt % of lactam, lactone or carbonate and 20-85 wt % of amine. The ink prepared in the example is likely suspension rather than solution considering the dark color of the ink. Emulsifier which may do harm to the physical properties of patterns formed, should be added to the ink to sustain suspension, In addition, maintenance problems concerning nozzle clog caused by particles may arise.
• Prior arts published to date are listed below as Table 1 and Table 2.

• TABLE 1
  Patent Documents

  				Application
  				Date(Publication
  				or Registration
  No.	Country	Applicant(Inventor)	Title of Invention	No.)	Technical Features
  1)	US	Engelhard(Pascaline	metallized	1986, 9, 10(Pat. No.	Metal carboxylate,
  		Nguyen)	substrates and	4808274)	alcoholate,
  			process for		mercaptide,
  			producing		amino + carboxylate,
  					acyl + carboxylate,
  					alkoxide
  2)	US	(Michael G.	Seed layer compositions	1990, 4, 27(Pat. No.	metal bonded to
  		Firmstone,	containing	5059242)	hydrocarbon
  		et al)	organogold and		through thio,
  			organosilver		polythio,
  			compounds		carboxylate bridge
  3)	US	Degussa	Gold(I) mercapto-	1993, 4, 5(Pat. No. 5312480)	gold(I)mercaptocarboxyic
  		(Lotze;	carboxylic acid		acid ester
  		Marion)	esters, method of		used for ceramic
  			their preparation		gold decoration
  			and use
  4)	PCT	Parelec,	Material and	International Application	metal
  		Inc. (Kydd;	method for	1997, 9,	powder + MOD or
  		Paul H. □□)	printing high conductivity	12(international	ROM (reactive
  			electrical	publication	organic medium);
  			conductors and	WO98-37133)	MOD is defined as
  			other components		organic material
  			on thin film		bonded to metal
  			transistor arrays		through hetero
  					atoms such as O,
  					N, S, P, As and Se
  5)	US	Kovio, Inc	Nanoparticle	2002, 8, 9(Pat. No.	particulate ink
  		(Rockenberger;	synthesis and the	6878184)	prepared by
  		Joerg)	formation of inks		reducing MOD(or
  			therefrom		metal powder +
  					RMO) with
  					aldehydes
  6)	South	haeuncomtec	Organic silver	2003, 03, 28(Publication	5-40 wt % of
  	Korea	(Kwangchun-	composition,	No.	Ag + 10-20 wt % of
  		Jung)	preparing method	2004-84570)	(lactam, lacton or
  			therefor, inks		carbonate + 20-85 wt
  			prepared		% of amine
  			therefrom and
  			method for
  			forming
  			conductive circuit
  			with use thereof

• TABLE 2
  Nonpatent Documents

  No.	author	Title of Article	Publication date	Technical features
  1)	Teng, K. F.,	Liquid Ink Jet	IEEE Transactions	MOD is mentioned as organic
  	and	Printing with MOD	on	material bonded to metal
  	Vest, R. W.	Inks for Hybrid Microcircuits	Components, Hybrids	through hetero atoms such as
  			and Mamufacturing	O, N, S and P Specifically,
  			Technology,	silver neodecanoate and Au
  			12(4), 545-549,	amine 2-ethylhexoate is examplified.
  			1987	Dielectric ink and
  				resistance ink are mentioned
  2)	Lea	Direct Write Metallizations	2000, 8, 18 undergraduate	(hfa)Ag(COD),
  	Yancey	with	thesis of	(hfa)Cu(BTMS)
  		Organometallic	Berkely	and(hfa)Cu(VTMS) are
  		Inks	University	spayed or printed by inkjet
  				printing on heated glass
  				annealed and resistance are
  				tested
  3)	C. Curtis,	Metallizations by	To be presented at	(hfa)Ag(COD)
  		Direct-Write	the NCPV
  		Inkjet Printing	Program Review
  			Meeting Lakewood,
  			Colorado14-17
  			October 2001
  4)	Alex	Synthesis of Single	Peer-Reviewed	SrCu2O2 from MOD(copper
  	Martins	Phase SrCu2O2	science	formate and strontium acetate)
  	on	from Liquid	Journal 2004, 3, 3	is printed and annealed at
  		Precursors		770° C. used as photosemi-
  				conductor of solar cell
  5)	Kevin	Ink-Jet Printing,	Macromol. Rapid	laminating polymer
  	Cheng,*	Self-Assembled	Commun. 2005,	electrolytes PAA and PAH by
  		Polyelectrolytes, and	26, 247-264	PEM technology and
  		Electroless Plating:		patterning the laminar with
  				catalyst Na2PdCl4 and
  				deposit in copper bath
  				electolessly. lower metalization
  				is possible

DISCLOSURE OF INVENTIONTechnical Problem
• The object of the present invention is to provide silver organo-sol ink for forming electrically conductive patterns with good physical properties.
• The other object of the present invention is to provide silver organo-sol ink, which can be applied to traditional printing methods including inkjet-printing.
Technical Solution
• The present invention provides silver organo-sol ink of solution type for forming electrically conductive pattern comprising effective amount of silver aromatic carboxylate defined as Formulas 1; and solvent dissolving said silver aromatic carboxylate
• 
• in which R₁, R₂, R₃, R₄and R₅are respectively COO⁻Ag⁺, H, OH or C1 to C9 alkyl. Herein, “organo-sol” means that silver exist as solution state bound to organic material.
• The said dissolving solvent desirably consists of a reactive organic solvent, which can form chelate or complex with silver, and polar or nonpolar diluent solvent for control of viscosity. The reactive organic solvents, which can form chelate or complex with silver, are, for example, organic solvents having keton, mercapto, carboxyl, aniline or sulfurous functional group, substituted or unsubstituted. The silver aromatic carboxylate is typically 5˜70 wt % of the total ink composition.
• As a preferred embodiment, the present invention provides silver organo-sol ink of solution type comprising 10 to 50 wt % of silver aromatic carboxylate defined as Formulas 1a; 10 to 60 wt % of reactive organic solvent selected from the group consisting of amine substituted by one or more C1 to C6 hydroxy alkyl and C2 to C16 aliphatic thiol, linear or branched; and residual polar or nonpolar diluent solvent
• 
• in which R₁, R₂, R₃, R₄and R₅are respectively H, OH or C1 to C9 alkyl. Said silver aromatic carboxylate defined as Formulas 1a is most desirably silver benzoate when R₁, R₂, R₃, R₄and R₅are respectively H.
• As another preferred embodiment, the present invention provides silver organo-sol ink of solution type comprising 10 to 50 wt % of silver aromatic carboxylate defined as Formulas 1b; 10 to 60 wt % of reactive organic solvent selected from the group consisting of amine substituted by one or more C1 to C6 hydroxy alkyl and C2 to C16 aliphatic thiol, linear or branched; and residual polar or nonpolar diluent solvent
• 
• in which one among R₁, R₂, R₃, R₄and R₅is COO⁻Ag⁺the others are respectively H, OH or C1 to C9 alkyl, but desirably R₃is COO⁻Ag⁺. Said silver aromatic carboxylate defined as Formulas 1b is most desirably silver phthalate when R₃is COO⁻Ag⁺and the others R₁, R₂, R₃, R₄and R₅are respectively H.
• As another preferred embodiment, the present invention provides silver organo-sol ink of solution type comprising 10 to 50 wt % of silver aromatic carboxylate defined as Formulas 1c; 10 to 60 wt % of reactive organic solvent selected from the group consisting of amine substituted by one or more C1 to C6 hydroxy alkyl and C2 to C16 aliphatic thiol, linear or branched; and residual polar or nonpolar diluent solvent
• 
• in which two or more among R₁, R₂, R₃, R₄and R₅are COO⁻Ag⁺, the others are respectively H, OH or C1 to C9 alkyl, but desirably R₂and R₄are COO⁻Ag⁺. Said silver aromatic carboxylate defined as Formulas 1c is most desirably silver trimesate when R₂and R₄are COO⁻Ag⁺and the others R₁, R₃and R₅are respectively H.
• The organo-sol ink of the present invention may further comprise surfactants and/or viscosity controlling agents. In addition, it may comprise further nonconductive polymeric or glassy material as matrix or flux material for silver conductor. The organo-sol ink of the present invention can be applied not only to processes for display manufacturing such as PDP and Rfid but also to other processes such as solar cells wherein conductive patterns are required.
• Silver aromatic carboxylate defined as Formulas 1 has higher contents of silver, especially, silver benzoate has about 47 wt % of silver per mole of the compound. It has a merit of higher content of metalized silver even if small quantity is adopted.
• Silver aromatic carboxylate defined as Formulas 1 in the organo-sol ink of the present invention desirably ranges from 5 wt % to 70 wt % of the total ink composition since silver content becomes small below 5 w % and making solution with it becomes difficult above 70 wt %. The preferred range is 10 wt % to 50 wt %. The most preferred range is 20 wt % to 40 wt %. Silver aromatic carboxylate defined as Formulas 1is prepared by reacting silver inorganic acid salt such as silver nitrate with alkali metal salt corresponding to Formulas 1 with silver replaced by alkali metal.
• The said reactive organic solvent is broadly organic solvent which can form chelate or complex with silver through hetero atom N, O and S ,more preferably, hydrocarbons having keton, mercapto, carboxyl, aniline or sulfurous functional group, substituted or unsubstituted. The most preferred are monoethanolamine, diethanolamine and triethanolamine. The organo-sol ink of the present invention has light color but is basically clear. The viscosity of the initial solution which is prepared by dissolving the silver organic salt in a reactive organic solvent such as ethanolamine ranges about 10,000 to 100,000 cp, and thus it can be used in screen-printing, offset-printing and imprinting. It also can be diluted by diluent such as ethanol or water according to the object of use.
• Silver organo-sol prepared by dissolving silver aromatic carboxylate in reactive solvent, for example, amine substituted by one or more ethanol may be further diluted with ethylene glycol or water to be deposited on a hydrophilic substrate. On the other hand, it may be diluted with an alcohol of short chain alcohol such as ethanol to be deposited on a substrate having a hydrophobic metal oxide film thereon. It is presumed that the solubility increases drastically because the reactive organic solvent forms complex with the silver aromatic carboxylate by chelating or coordinate covalent bonding.
• A preferred nonpolar diluent solvent is an aliphatic or aromatic hydrocarbon or mixture thereof. A preferred polar diluent solvent is water or C1 to C12, saturated or unsaturated, mono to tri functional aliphatic alcohol. The organic solvent, for example, is 2-methoxy ethanol, 1,2-hexanediol, benzene, toluene, xylene, dimethylcarbithol, kerosene ethanol, methanol, 2-propanol, chloroform or ethylene glycol.
• The solution type ink of the present invention can be used for forming conductive patterns in flat panel display such as plasma display panel(PDP) to reduce the numbers of steps for pattern forming drastically. Especially, since metalized silver from the silver organo-sol ink of the present invention is stable at relatively higher temperature, for example, 450˜600° C., more specifically, at 480˜580° C., the silver ink is appropriate for conductive pattern forming in PDP manufacturing wherein sealing and sintering of barrier ribs is carried out around the temperature range.
ADVANTAGEOUS EFFECTS
• By the present invention, silver organo-sol ink of solution type basically having higher content of silver is obtained. The solution type ink of the present invention can be used for forming conductive patterns in flat panel display such as plasma display panel(PDP) to reduce the numbers of steps for pattern forming drastically.
BRIEF DESCRIPTION OF THE DRAWINGS
• FIG. 1 shows IR spectrometer graphs of silver powder, triethanolamine and silver organo-sol ink used by Example 1.
• FIG. 2 is a photograph showing contact angle against glass of silver organo-sol ink prepared by Example 1.
• FIG. 3 shows from above respectively (a) SEM images of two scales regarding a sample after heat-treatment at 550° C. for 10 minutes prepared by Example 3, (b) SEM images of two scales regarding a sample prepared by Example 4 after heat-treatment at 550° C. for 10 minutes and (c) SEM images of two scales regarding a sample prepared by Example 5 after heat-treatment at 550° C. for 10 minutes.
BEST MODE FOR CARRYING OUT THE INVENTION
• The present invention is illustrated by examples below. However, such examples presented for the purpose of illustration does not serve as a basis to decide the scope of the invention.
Example 1
• 50 mmol benzoic acid is dissolved in 50 mL of methanol. 50 mmol NaOH dissolved in 50 mL water is added slowly to the benzoic acid solution prepared while stirring to obtain sodium benzoate. 50 mmol silver nitrate dissolved in 50 mL water is added to the sodium benzoate solution, and then white precipitate forms fast. The precipitate is washed to remove unreacted silver nitrate and NaOH with water, filtered and washed several times to remove unreacted benzoic acid with methanol. The filtrant white silver benzoate is sensitive to light and should be dried and stored in dark room or under yellow light.
• 0.07 mol prepared powder of silver benzoic acid (molecular weight: about 228 g/mol) is dissolved in 0.14 mol triethanolamine and 40 mL ethylene is added to control viscosity. The viscosity of the solution prepared is 15cPs at 25° C. by Brookfield viscometer. Absorption bands around 1000 and 1300 cm⁻¹characteristic peak of silver solution are also observed by IR spectrometer.
• The contact angle of the solution against glass substrate is observed to be about 40° C. The glass is coated by the ink solution prepared with a bar coater, heat-treated at 150° C. for 10 minutes and resistance is measured to be 5.5×10⁻⁶Ω□□. The coated glass is further heat treated at 500° C. The resistance is 2.505×10⁻⁶Ω□□. The solid content of the solution ink is about 63 wt % of the total solution since the weights of the solution coated and residual solid after heat-treatment at 500° C. are respectively 0.5804 g and 0.3656 g.
Example 2
• 50 mmol benzoic acid is dissolved in 50 mL of methanol. 50 mmol NaOH dissolved in 50 mL water is added slowly to the benzoic acid solution prepared while stirring to obtain sodium benzoate. 50 mmol silver nitrate dissolved in 50 mL water is added to the sodium benzoate solution, and then white precipitate forms fast. The precipitate is silver benzoate formed by exchange of Na+ and Ag+ by ionization tendency, washed to remove unreacted silver nitrate and NaOH with water, filtered and further washed several times to remove unreacted benzoic acid with methanol, and dried at 50° C. to obtain final silver benzoate.
• 0.07 mol prepared powder of silver benzoic acid (molecular weight: about 228g/mol) is dissolved in 0.14 mol OT (octanethiol). Xylene is added so that the viscosity of the solution prepared should be between 13˜15 cps at 25° C. by Brookfield viscometer, and the solution is agitated for 30 minute more.
• Glass substrate is coated by the ink solution prepared with a bar coater, heat-treated 150° C. for 10 minutes and resistance is measured. The coated glass is further heat-treated at 500° C. The resistance is measured. By the residual solid content of the solution ink after heat-treatment at 500° C. the final silver content is decided. Volumetric resistance with thickness of coated film is measured. The resistance is 2.75×10⁻⁶Ω□□.The solid content of the solution ink is about 54.3 wt % of the total solution. Amounts of reagents and measured value are listed in Table 3.
Example 3
• 50 mmol benzoic acid is dissolved in 50 mL methanol. 50 mmol NaOH dissolved in 50 mL water is added slowly to the benzoic acid solution prepared while stirring to obtain sodium benzoate. 50 mmol silver nitrate dissolved in 50 mL water is added to the sodium benzoate solution, and then white precipitate forms fast. The precipitate is silver benzoate formed by exchange of Na+ and Ag+ by ionization tendency, washed to remove unreacted silver nitrate and NaOH with water, filtered and further washed several times to remove unreacted benzoic acid with methanol, and dried at 50° C. to obtain final silver benzoate.
• 0.21 mol prepared powder of silver benzoic acid (molecular weight: about 228 g/mol) is dissolved in 0.42 mol TEA (triethanol amine). Ethanol is added so that the viscosity of the solution prepared should be 15 cps at 25° C. by Brookfield viscometer, and the solution is agitated for 30 minute more.
• Glass substrate is coated by the ink solution prepared with a bar coater, heat-treated 150° C. for 10 minutes and resistance is measured. The coated glass is further heat treated at 550° C. The resistance is measured. The microstructure is shown inFIG. 3 AccordingFIG. 3, silver particles are fused together after heat-treatment at 550° C. even on 10,000 times enlarged images. By the residual solid content of the solution ink after heat-treatment at 550° C. the final silver content is decided. Volumetric resistance with thickness of coated film is measured. Amounts of reagents and measured value are listed in Table 3.
Example 4
• Example 4 is carried out the same way as Example 2 except that terephthalic acid is used instead of benzoic acid. The microstructure is shown inFIG. 3. AccordingFIG. 3, silver particles are fused together after heat-treatment at 550° C. even on 10,000 times enlarged images. Volumetric resistance with thickness of coated film is measured. Amounts of reagents and measured value are listed in Table 3.
Example 5
• Example 5 is carried out the same way as Example 2 except that trimesic acid is used instead of benzoic acid. The microstructure is shown inFIG. 3. AccordingFIG. 3, silver particles are fused together after heat-treatment at 550° C. even on 10,000 times enlarged images. Volumetric resistance with thickness of coated film is measured. Amounts of reagents and measured value are listed in Table 3.

• TABLE 3
  	Reactive
  Precursor	solvent	Solvent	resistance

  	Amount		Amount		Amount	(10−6Ω ·
  Example	(mol)	name	(mol)	Name	(ml) or (g)	□)

  1. Ag 1	0.07	TEA	0.14	xylene	40	(ml)	2.505
  2. Ag 1	0.07	OT	0.14	EtOH	40	(ml)	2.75
  3. Ag 1	0.21	EA	0.42	EtOH	58	(g)	9.9
  4. Ag 2	0.21	EA	0.84	EtOH	186	(g)	2.7
  5. Ag 3	0.21	EA	1.26	EtOH	150	(g)	1.1
  *Ag 1; One COOAg Ag 2; Two COOAg Ag 3; Three COOAg

INDUSTRIAL APPLICABILITY
• The solution type ink of the present invention can be used for forming conductive patterns by traditional printing technology, especially by inkjet-printing, in flat panel display such as plasma display panel(PDP) to reduce the numbers of steps for pattern forming drastically.

Claims (18)

1. Silver organo-sol ink of solution type for forming electrically conductive pattern comprising effective amount of silver aromatic carboxylate defined as Formulas 1; and solvent dissolving said silver aromatic carboxylate

in which R₁, R₂, R₃, R₄and R₅are respectively COO⁻Ag⁺, H, OH or C1 to C9 alkyl.

2. Silver organo-sol ink of solution type according toclaim 1, wherein said solvent consists of a reactive organic solvent which can form chelate or complex with silver and polar or nonpolar diluent solvent for control of viscosity.

3. Silver organo-sol ink of solution type according toclaim 2, wherein said reactive organic solvent is a hydrocarbon having keton, mercapto, carboxyl, aniline or sulfurous functional group.

4. Silver organo-sol ink of solution type according toclaim 3, wherein said nonpolar diluent solvent is an aliphatic or aromatic hydrocarbon and said polar diluent solvent is water or C1 to C12, saturated or unsaturated, mono to tri functional aliphatic alcohol.

5. Silver organo-sol ink of solution type according toclaim 4, wherein said silver aromatic carboxylate is 5 to 70 wt % of the total silver organo-sol ink.

6. Silver organo-sol ink of solution type according toclaim 5, wherein said silver aromatic carboxylate defined as Formulas 1a is 10 to 50 wt % of the total silver organo-sol ink, said reactive organic solvent selected from the group consisting of amine substituted by one or more C1 to C6 hydroxy alkyl and C2 to C16 aliphatic thiol, is 10 to 60 wt % of the total silver organo-sol ink

in which R₁, R₂, R₃, R₄and R₅are respectively H, OH or C1 to C9 alkyl.

7. Silver organo-sol ink of solution type according toclaim 6, wherein said silver aromatic carboxylate defined as Formulas 1a is silver benzoate.

8. Silver organo-sol ink of solution type according toclaim 5, wherein said silver aromatic carboxylate defined as Formulas 1b is 10 to 50 wt % of the total silver organo-sol ink, said reactive organic solvent selected from the group consisting of amine substituted by one or more C1 to C6 hydroxy alkyl and C2 to C16 aliphatic thiol, is 10 to 60 wt % of the total silver organo-sol ink

in which one R₁, R₂, R₃, R₄and R₅is COO⁻Ag⁺and the others are respectively H, OH or C1 to C9 alkyl.

9. Silver organo-sol ink of solution type according toclaim 8, wherein R₃is COO⁻Ag⁺and R₁, R₂, R₄and R₅are respectively H, OH or C1 to C9 alkyl.

10. Silver organo-sol ink of solution type according toclaim 9, wherein said silver aromatic carboxylate defined as Formulas 1b is silver phthalate.

11. Silver organo-sol ink of solution type according toclaim 5, wherein said silver aromatic carboxylate defined as Formulas 1b is 10 to 50 wt % of the total silver organo-sol ink, said reactive organic solvent selected from the group consisting of amine substituted by one or more C1 to C6 hydroxy alkyl and C2 to C16 aliphatic thiol, is 10 to 60 wt % of the total silver organo-sol ink

in which two or more among R₁, R₂, R₃, R₄and R₅are COO⁻Ag⁺, the others are respectively H, OH or C1 to C9 alkyl.

12. Silver organo-sol ink of solution type according toclaim 11, wherein R₂and R₄are COO⁻Ag⁺and R₁, R₃and R₅are respectively H, OH or C1 to C9 alkyl.

13. Silver organo-sol ink of solution type according toclaim 12, wherein said silver aromatic carboxylate defined as Formulas 1c is silver trimesate.

14. Silver organo-sol ink of solution type according to any one ofclaim 1 toclaim 13, wherein said silver organo-sol ink is used for electrically conductive patterns by inkjet-printing.

15. Silver organo-sol ink of solution type according toclaim 14, wherein said silver aromatic carboxylate is 20 to 40 wt % of the total silver organo-sol ink.

16. Silver organo-sol ink of solution type according toclaim 15, wherein said reactive solvent is ethanolamine, diethanolamine or triethanolamine.

17. Silver organo-sol ink of solution type according toclaim 16, wherein said nonpolar diluent solvent is an aliphatic or aromatic hydrocarbon or mixture thereof said polar diluent solvent is water or C1 to C12 saturated or unsaturated mono to tri functional aliphatic alcohol.

18. Silver organo-sol ink of solution type according toclaim 17, wherein said nonpolar diluent solvent is benzene, toluene, xylene.

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